The lithium ion battery possesses advantages of high energy, long life, little pollution, and etc, so it is widely applied in a variety of fields such as portable electronic facilities, electric automobiles, and etc. Positive electrode materials play an important role in the production of the lithium ion battery, since the quality of the positive electrode material directly determines the performances of the final secondary batteries whose cost also depends on the cost of the positive electrode material.
The positive electrode materials for the lithium ion battery widely studied presently include transition metal oxides LiCoO2 and LiNiO2 with layer structure, LiMn2O4 with spinel structure, and LiFePO4 with olivine structure. Each of the four materials has its advantages and disadvantages. For example, LiCoO2 possesses excellent comprehensive performance, so it is the sole positive electrode material commercialized in a large scale presently, but it has the disadvantages of high price, low capacity and high toxicity, and may bring on some safety problems. LiNiO2 possesses the advantages of low cost and high capacity, but it is difficult to prepare, and the prepared material has poor uniformity and reproducibility performances, and may bring on severe safety problems. LiMn2O4 with spinel structure possesses the advantages of low cost and good security, but its cycle performance, especially at a high temperature, is poor, and it is somewhat soluble in the electrolyte, resulting in a poor storage performance.
It is discovered recently that the comprehensive performances of the material may be highly improved and the cost may be lowered by partly replacing cobalt with nickel and manganese. For example, a novel positive electrode material, LiNi1/3Co1/3Mn1/3O2, possesses most advantages of each positive electrode material LiCoO2, LiNiO2, and LiMn2O4, such as low cost, high voltage platform, large reversible capacity (160-190 mAh/g), stable structure, good cycle performance, and mild preparation conditions. The preparation and performance of LiNixMnyCo1-x-yO2 have been reported in many literatures, and the high temperature solid phase method and coprecipitation method are generally used to prepare the material. For example, CN 1595680A discloses a process for preparing a positive electrode material for lithium ion batteries, which comprises mixing the coprecipitated hydroxide, carbonate or oxide of nickel, manganese and at least one of cobalt, titanium, and aluminum with lithium hydroxide or lithium carbonate; loosely piling-up the mixture and pelleting on a press machine; calcining at high temperature in solid phase; and pulverizing after cooling to obtain the positive electrode material.
CN 1547277A discloses a manganese-nickel-cobalt composite lithium-embedded oxide and its preparation process, which comprises preparing a mixed solution consisting of a manganese salt, nickel salt, and cobalt salt according to a mole ratio of Mn:Ni:Co=1:(0.8-1.2):(0.1-1), heating to 20-90° C., adding excessive alkali under stirring, separating the composite manganese-nickel-cobalt hydroxide obtained by precipitation, calcining the above composite hydroxide at 100-700° C. to yield a composite manganese-nickel-cobalt oxide, mixing a lithium-source substance into the composite manganese-nickel-cobalt oxide, calcining the mixture at 700-1000° C. for 6-36 hours, cooling, and pulverizing to yield the final product.
CN 1614801A discloses a process for preparing a multielement composite positive electrode material for the lithium ion battery, which comprises using compounds of nickel, cobalt, and manganese as feed stocks to prepare a solution with a total concentration of 0.05-10 mol/L, mixing said solution with an alkaline solution of 0.05-10 mol/L, adding an additive at the same time, stirring to form a uniform precipitate, drying the precipitate, mixing it with a lithium compound, pulverizing in a ball-mill, and calcining the mixture at 400-1000° C. for 1-30 hours to yield the product. The additive used in this process is a surfactant sodium dodecyl benzene sulfonate or PVP for suppressing the agglomeration of the crystal nuclei.
CN 1622371A discloses a process for preparing high density spheric lithium nickel-cobalt-manganate used as an positive electrode material for the lithium ion battery, which comprises continuously pumping a mixed aqueous solution of a nickel salt, cobalt salt, and manganese salt, an aqueous solution of sodium hydroxide, and an aqueous solution of ammonia respectively into a reactor equipped with a stirrer, reacting the above solutions while controlling the flow rates of the mixed aqueous solution of nickel-cobalt-manganese salts and the aqueous solution of ammonia and the reaction conditions to yield a spheric or near-spheric precursor of nickel-cobalt-manganese hydroxide Ni1/3Co1/3Mn1/3(OH)2, uniformly mixing it with lithium carbonate after washing and drying, and thermally treating in air at 750-950° C. for 8-48 hours to yield spheric lithium nickel-cobalt-manganate.
The above various processes possess the advantages of low cost, mild preparation conditions, low price, and etc, and the structure of the prepared positive electrode materials is stable, but there is a common shortcoming, i.e. the tap densities of the prepared positive electrode materials are low, leading to low volume specific capacities of the batteries.